Oxidizing aqueous cleaner for the removal of post-etch residues

ABSTRACT

An oxidizing aqueous cleaning composition and process for cleaning post-plasma etch residue and/or hardmask material from a microelectronic device having said residue thereon. The oxidizing aqueous cleaning composition includes at least one oxidizing agent, at least one oxidizing agent stabilizer comprising an amine species selected from the group consisting of primary amines, secondary amines, tertiary amines and amine-N-oxides, optionally at least one co-solvent, optionally at least one metal-chelating agent, optionally at least one buffering species, and water. The composition achieves highly efficacious cleaning of the residue material from the microelectronic device while simultaneously not damaging the interlevel dielectric and metal interconnect material also present thereon.

FIELD OF THE INVENTION

The present invention relates to aqueous oxidizing compositions for theremoval of post-etch residue and/or titanium-containing hardmaskmaterial from microelectronic devices and methods of making and usingthe same, wherein the oxidizing compositions have a high selectivity fortitanium-containing materials relative to the interlevel dielectric(ILD) and metallic interconnect materials on the microelectronic device.

DESCRIPTION OF THE RELATED ART

Interconnect circuitry in semiconductor circuits consists of conductivemetallic circuitry surrounded by insulating dielectric material. In thepast, silicate glass vapor-deposited from tetraethylorthosilicate (TEOS)was widely used as the dielectric material, while alloys of aluminumwere used for metallic interconnects.

Demand for higher processing speeds has led to smaller sizing of circuitelements, along with the replacement of TEOS and aluminum alloys byhigher performance materials. Aluminum alloys have been replaced bycopper or copper alloys due to the higher conductivity of copper. TEOSand fluorinated silicate glass (FSG) have been replaced by the so-calledlow-k dielectrics, including low-polarity materials such as organicpolymers, hybrid organic/inorganic materials, organosilicate glass(OSG), and carbon-doped oxide (CDO) glass. The incorporation ofporosity, i.e., air-filled pores, in these materials further lowers thedielectric constant of the material.

During dual-damascene processing of integrated circuits,photolithography is used to image a pattern onto a device wafer.Photolithography techniques comprise the steps of coating, exposure, anddevelopment. A wafer is coated with a positive or negative photoresistsubstance and subsequently covered with a mask that defines patterns tobe retained or removed in subsequent processes. Following the properpositioning of the mask, the mask has directed therethrough a beam ofmonochromatic radiation, such as ultraviolet (UV) light or deep UV (DUV)light (≈250 nm or 193 nm), to make the exposed photoresist material moreor less soluble in a selected rinsing solution. The soluble photoresistmaterial is then removed, or “developed,” thereby leaving behind apattern identical to the mask.

Thereafter, gas-phase plasma etching is used to transfer the patterns ofthe developed photoresist coating to the underlying layers, which mayinclude hardmask, interlevel dielectric (ILD), and/or etch stop layers.Post-plasma etch residues are typically deposited on theback-end-of-the-line (BEOL) structures and if not removed, may interferewith subsequent silicidation or contact formation. Post-plasma etchresidues typically include chemical elements present on the substrateand in the plasma gases. For example, if a TiN hardmask is employed,e.g., as a capping layer over ILD, the post-plasma etch residues includetitanium-containing species, which are difficult to remove usingconventional wet cleaning chemistries. Moreover, conventional cleaningchemistries often damage the ILD, absorb into the pores of the ILDthereby increasing the dielectric constant, and/or corrode the metalstructures. For example, buffered fluoride and solvent-based chemistriesfail to completely remove TiN and Ti-containing residues, whilehydroxylamine-containing and ammonia-peroxide chemistries corrodecopper.

In addition to the desirable removal of titanium-containing hardmaskand/or titanium-containing post-plasma etch residue, additionalmaterials that are deposited during the post-plasma etch process such aspolymeric residues on the sidewalls of the patterned device andcopper-containing residues in the open via structures of the device arealso preferably removed. To date, no single wet cleaning composition hassuccessfully removed all of residue and/or hardmask material whilesimultaneously being compatible with the ILD, other low-k dielectricmaterials, and metal interconnect materials.

The integration of new materials, such as low-k dielectrics, intomicroelectronic devices places new demands on cleaning performance. Atthe same time, shrinking device dimensions reduce the tolerance forchanges in critical dimensions and damage to device elements. Etchingconditions can be modified in order to meet the demands of the newmaterials. Likewise, post-plasma etch cleaning compositions must bemodified. Importantly, the cleaner should not damage the underlyingdielectric material or corrode metallic interconnect materials, e.g.,copper, tungsten, cobalt, aluminum, ruthenium, and silicides thereof, onthe device.

Towards that end, it is an object of the present invention to provideimproved aqueous compositions for the selective and effective removal oftitanium-containing post-plasma etch residue, polymeric sidewallresidue, copper-containing via residue and/or titanium-containinghardmask layers from microelectronic devices, said compositions beingcompatible with ILD and metal interconnect materials.

It is another object of the present invention to provide improvedaqueous compositions having an extended bath-life relative toconventional peroxide-containing cleaning compositions.

SUMMARY OF THE INVENTION

The present invention generally relates to cleaning compositions andmethods of making and using same. One aspect of the invention relates toan oxidizing aqueous composition and process for cleaning post-plasmaetch residue and/or titanium-containing hardmask from microelectronicdevices having said residue and/or hardmask thereon, whilesimultaneously not compromising the metallic and ILD materials on themicroelectronic device surface. The oxidizing aqueous cleaningcompositions of the invention include at least one oxidizing agent, atleast one oxidizing agent stabilizer comprising an amine speciesselected from the group consisting of primary amines, secondary amines,tertiary amines and amine-N-oxides, optionally at least one organicco-solvent, optionally at least one metal-chelating agent, optionally atleast one buffering species, and water.

In one aspect, the invention relates to an oxidizing aqueous cleaningcomposition, comprising at least one oxidizing agent, at least oneoxidizing agent stabilizer comprising an amine species selected from thegroup consisting of primary amines, secondary amines, tertiary aminesand amine-N-oxides, optionally at least one organic co-solvent,optionally at least one metal-chelating agent, optionally at least onebuffering species, and water, wherein said aqueous cleaning compositionis suitable for cleaning post-plasma etch residue and/or hardmaskmaterial from a microelectronic device having said residue and/orhardmask thereon.

In another aspect, the invention relates to a kit comprising, in one ormore containers, one or more of the following reagents for forming anoxidizing aqueous cleaning composition, said one or more reagentsselected from the group consisting of at least one oxidizing agent, atleast one oxidizing agent stabilizer comprising an amine speciesselected from the group consisting of primary amines, secondary amines,tertiary amines and amine-N-oxides, optionally at least one co-solvent,optionally at least one chelating agent, optionally at least onebuffering species, and water, and wherein the kit is adapted to form anoxidizing aqueous cleaning composition suitable for cleaning post-plasmaetch residue and/or hardmask material from a microelectronic devicehaving said residue and/or material thereon.

In still another aspect, the present invention relates to a method ofremoving post-plasma etch residue and/or hardmask material from amicroelectronic device having said residue and/or hardmask thereon, saidmethod comprising contacting the microelectronic device with anoxidizing aqueous cleaning composition for sufficient time to at leastpartially clean said residue and/or hardmask from the microelectronicdevice, wherein the oxidizing aqueous cleaning composition includes atleast one oxidizing agent, at least one oxidizing agent stabilizercomprising an amine species selected from the group consisting ofprimary amines, secondary amines, tertiary amines and amine-N-oxides,optionally at least one organic co-solvent, optionally at least onemetal-chelating agent, optionally at least one buffering species, andwater.

Still another aspect of the invention relates to a oxidizing aqueouscleaning composition, comprising at least one oxidizing agent, at leastone oxidizing agent stabilizer comprising an amine species selected fromthe group consisting of primary amines, secondary amines, tertiaryamines and amine-N-oxides, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water,wherein said aqueous cleaning composition is suitable for cleaningpost-plasma etch residue and/or hardmask material from a microelectronicdevice having said residue and/or hardmask thereon.

In yet another aspect, the invention relates to an oxidizing aqueouscleaning composition, comprising hydrogen peroxide, at least oneamine-N-oxide, optionally at least one organic co-solvent, optionally atleast one metal-chelating agent, optionally at least one bufferingspecies, and water, wherein said aqueous cleaning composition issuitable for cleaning post-plasma etch residue and/or hardmask materialfrom a microelectronic device having said residue and/or hardmaskthereon.

Still another aspect of the invention relates to an oxidizing aqueouscleaning composition comprising hydrogen peroxide, at least oneamine-N-oxide, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water,wherein said aqueous cleaning composition is suitable for cleaningpost-plasma etch residue and/or hardmask material from a microelectronicdevice having said residue and/or hardmask thereon.

Another aspect of the invention relates to an oxidizing aqueous cleaningcomposition comprising hydrogen peroxide, at least one amine-N-oxide,diethylene glycol butyl ether, 1,2,4-triazole, tetramethylammoniumhydroxide, citric acid, and water, wherein said aqueous cleaningcomposition is suitable for cleaning post-plasma etch residue and/orhardmask material from a microelectronic device having said residueand/or hardmask thereon.

Yet aspect of the invention relates to an oxidizing aqueous cleaningcomposition comprising hydrogen peroxide, at least one amine-N-oxide,diethylene glycol butyl ether,1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid, tetramethylammoniumhydroxide, boric acid, and water, wherein said aqueous cleaningcomposition is suitable for cleaning post-plasma etch residue and/orhardmask material from a microelectronic device having said residueand/or hardmask thereon.

A further aspect of the invention relates to an oxidizing aqueouscleaning composition comprising hydrogen peroxide,1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid, boric acid, andwater, wherein said aqueous cleaning composition is suitable forcleaning post-plasma etch residue and/or hardmask material from amicroelectronic device having said residue and/or hardmask thereon.

A further aspect of the invention relates to a CMP shiny composition toremove barrier layer material from a microelectronic device substrate,said CMP slurry composition comprising abrasive, at least one oxidizingagent, at least one oxidizing agent stabilizer comprising an aminespecies selected from the group consisting of primary amines, secondaryamines, tertiary amines and amine-N-oxides, at least one metal-chelatingagent, optionally at least one organic co-solvent, optionally at leastone buffering species, and water, wherein said CMP slurry composition issuitable for the selective removal of barrier layer material relative tometal interconnect and dielectric material layers.

Another aspect of the invention relates to a method of removingpost-plasma etch residue from a microelectronic device having saidresidue thereon, said method comprising:

-   -   contacting the microelectronic device with an oxidizing aqueous        cleaning composition for sufficient time to at least partially        clean said residue from the microelectronic device, wherein the        oxidizing aqueous cleaning composition includes at least one        oxidizing agent, at least one oxidizing agent stabilizer        comprising an amine-N-oxide, optionally at least one organic        co-solvent, optionally at least one metal-chelating agent,        optionally at least one buffering species, and water; and    -   contacting the microelectronic device with a dilute hydrofluoric        acid solution for sufficient time to at least partially remove        post-plasma etch residue from a metal interconnect material.

Another aspect of the invention relates to an article of manufacturecomprising an aqueous cleaning composition, a microelectronic device,and post-plasma etch residue and/or hardmask material, wherein theaqueous composition includes at least one oxidizing agent, at least oneoxidizing agent stabilizer comprising an amine species selected from thegroup consisting of primary amines, secondary amines, tertiary aminesand amine-N-oxides, optionally at least one organic co-solvent,optionally at least one metal-chelating agent, optionally at least onebuffering species, and water.

In a further aspect, the present invention relates to a method ofmanufacturing a microelectronic device, said method comprisingcontacting the microelectronic device with an oxidizing aqueous cleaningcomposition for sufficient time to at least partially remove post-plasmaetch residue and/or hardmask material from the microelectronic devicehaving said residue and/or material thereon, wherein the oxidizingaqueous composition includes at least one oxidizing agent, at least oneoxidizing agent stabilizer comprising an amine species selected from thegroup consisting of primary amines, secondary amines, tertiary aminesand amine-N-oxides, optionally at least one organic co-solvent,optionally at least one metal-chelating agent, optionally at least onebuffering species, and water.

Yet another aspect of the invention relates to improved microelectronicdevices, and products incorporating same, made using the methods of theinvention comprising cleaning of post-plasma etch residue and/orhardmask material from the microelectronic device having said residueand/or material thereon, using the methods and/or compositions describedherein, and optionally, incorporating the microelectronic device into aproduct.

Other aspects, features and advantages of the invention will be morefully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A illustrates a microelectronic device following post-plasma etchprocessing, wherein the sidewalls of the ultra low-k dielectric includepolymeric residue and the copper via (or line) includescopper-containing residue thereon.

FIG. 1B illustrates the microelectronic device of FIG. 1A followingcleaning using the oxidizing aqueous cleaning compositions of thepresent invention, wherein the polymeric residue, the copper-containingresidue, and the TiN hardmask has been removed.

FIG. 2 is an FTIR spectrograph of a blanketed porous-CDO wafer beforeand after cleaning the wafer with formulation E of the presentinvention.

FIG. 3 illustrates the percentage of hydrogen peroxide present informulations E and F of the present invention as a function of thelogarithm of time.

FIG. 4 illustrates the etch rate of PVD deposited copper in Å min⁻¹ as afunction of the pH of the buffered cleaning composition.

FIG. 5 illustrates the capacitance of a BD2 control wafer relative tothe capacitance of a BD2 control wafer following immersion inFormulations O and I at 55° C. for 5 minutes.

FIG. 6 illustrates the percentage of hydrogen peroxide present invariations of formulation S of the present invention as a function oftime.

FIG. 7 illustrates the pH of variations of formulation S of the presentinvention as a function of time.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

One aspect of the present invention relates to cleaning compositionscomprising at least one oxidizer, preferably hydrogen peroxide, and atleast one oxidizer stabilizer, preferably an amine-N-oxide. Preferably,the invention relates to oxidizing aqueous compositions for cleaningtitanium-containing post-etch residue, polymeric sidewall residue,copper-containing via and line residue and/or hardmask layers frommicroelectronic devices having said residue and/or layers thereon (see,for example, FIGS. 1A and 1B), said compositions being compatible withultra low-k (ULK) dielectric materials, such as OSG and porous-CDO, andthe metallic interconnect materials, e.g., copper and cobalt, on themicroelectronic device surface.

For ease of reference, “microelectronic device” corresponds tosemiconductor substrates, flat panel displays, andmicroelectromechanical systems (MEMS), manufactured for use inmicroelectronic, integrated circuit, or computer chip applications. Itis to be understood that the term “microelectronic device” is not meantto be limiting in any way and includes any substrate that willeventually become a microelectronic device or microelectronic assembly.

As defined herein, “oxidizing agent stabilizer” corresponds to a specieswhich extends the bath-life of the oxidizing agent and is compatiblewith metal interconnect material (e.g., copper) present on the surfaceof the microelectronic device. Preferably, in the presence of theoxidizing agent stabilizer, no more than 10% of the oxidizing agentdecomposes over a period of 24 hours at temperatures in a range fromabout 30° C. to about 50° C., more preferably no more than 5% over thesame period, most preferably no more than 2% over the same period.

“Post-etch residue” and “post-plasma etch residue,” as used herein,corresponds to material remaining following gas-phase plasma etchingprocesses, e.g., BEOL dual-damascene processing. The post-etch residuemay be organic, organometallic, organosilicic, or inorganic in nature,for example, silicon-containing material, hardmask capping layermaterial (e.g., titanium-containing material), nitrogen-containingmaterial, oxygen-containing material, polymeric residue material,copper-containing residue material, etch gas residue such as chlorineand fluorine, and combinations thereof.

As defined herein, “low-k dielectric material” corresponds to anymaterial used as a dielectric material in a layered microelectronicdevice, wherein the material has a dielectric constant less than about3.5. Preferably, the low-k dielectric materials include low-polaritymaterials such as silicon-containing organic polymers,silicon-containing hybrid organic/inorganic materials, organosilicateglass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide,and carbon-doped oxide (CDO) glass. It is to be appreciated that thelow-k dielectric materials may have varying densities and varyingporosities.

As defined herein, the term “polymeric sidewall residue” corresponds tothe residue that remains on the sidewalls of the patterned devicesubsequent to post-plasma etching processes. The residue issubstantially polymeric in nature however, it should be appreciated thatinorganic species, e.g., titanium, silicon and/or copper-containingspecies, may be present in the residue as well.

As used herein, “about” is intended to correspond to ±5% of the statedvalue.

As used herein, “suitability” for cleaning titanium-containing post-etchresidue, polymeric sidewall residue, copper-containing via and lineresidue and/or hardmask layers from a microelectronic device having saidresidue and/or material thereon corresponds to at least partial removalof said residue and/or material from the microelectronic device.Preferably, at least about 90% of one or more of the materials, morepreferably at least 95% of one or more of the materials, and mostpreferably at least 99% of one or more of the materials, is removed fromthe microelectronic device using the compositions of the invention.

“Hardmask capping layer” as used herein corresponds to materialsdeposited over dielectric material to protect same during the plasmaetch step. Hardmask capping layers are traditionally silicon nitrides,silicon oxynitrides and other similar compounds. Hardmask capping layersfurther contemplated herein include titanium nitride and titaniumoxynitride.

As defined herein, “amine species” includes primary amines, secondaryamines, tertiary amines and amine-N-oxide species.

Compositions of the invention may be embodied in a wide variety ofspecific formulations, as hereinafter more fully described.

In all such compositions, wherein specific components of the compositionare discussed in reference to weight percentage ranges including a zerolower limit, it will be understood that such components may be presentor absent in various specific embodiments of the composition, and thatin instances where such components are present, they may be present atconcentrations as low as 0.001 weight percent, based on the total weightof the composition in which such components are employed.

Titanium nitride compounds are notoriously difficult to etch using theammonia-containing compositions of the prior art. The present inventorsdiscovered a cleaning composition that is devoid of ammonia and/orstrong bases (e.g., NaOH, KOH, etc.) that effectively and selectivelyremoves titanium-containing residues, titanium-containing hardmaskmaterials (e.g., titanium nitride), or both, from the surface of amicroelectronic device having same thereon. In addition, the compositionhas a substantially longer bath-life relative to the ammonia-peroxidecompositions of the prior art and will substantially remove polymericsidewall residue and copper-containing residue. The compositions of theinvention may be formulated to substantially remove thetitanium-containing residue, the polymeric sidewall residue and/or thecopper-containing residue from the surface of the microelectronic devicewithout substantially damaging the underlying ILD, metal interconnectmaterials, and the hardmask layer. Alternatively, the composition may beformulated to additionally remove the hardmask layer from the surface ofthe microelectronic device without substantially damaging the underlyinglow-k dielectric and metal interconnect materials, as described indetail herein.

The oxidizing cleaning compositions of the invention include at leastone oxidizing agent, optionally at least one oxidizing agent stabilizercomprising an amine species selected from the group consisting ofprimary amines, secondary amines, tertiary amines and amine-N-oxides, atleast one organic co-solvent, at least one metal-chelating agent, atleast one buffering species, and water, for cleaning hardmask layersand/or post-plasma etch residues selected from the group consisting oftitanium-containing residues, polymeric residues, copper-containingresidues, and combinations thereof. In another embodiment, the oxidizingcleaning compositions of the invention include at least one oxidizingagent, at least one oxidizing agent stabilizer comprising an aminespecies selected from the group consisting of primary amines, secondaryamines, tertiary amines and amine-N-oxides, optionally at least oneorganic co-solvent, optionally at least one metal-chelating agent,optionally at least one buffering species, and water. In yet embodiment,the oxidizing cleaning compositions of the invention include at leastone oxidizing agent, at least one oxidizing agent stabilizer comprisingan amine species selected from the group consisting of primary amines,secondary amines, tertiary amines and amine-N-oxides, at least oneorganic co-solvent, optionally at least one metal-chelating agent,optionally at least one buffering species, and water. In still anotherembodiment, the oxidizing cleaning compositions of the invention includeat least one oxidizing agent, at least one oxidizing agent stabilizercomprising an amine species selected from the group consisting ofprimary amines, secondary amines, tertiary amines and amine-N-oxides, atleast one organic co-solvent, at least one metal-chelating agent, atleast one buffering species, and water.

In one aspect, the present invention relates to an oxidizing cleaningcomposition for cleaning hardmask layers and/or post-plasma etchresidues selected from the group consisting of titanium-containingresidues, polymeric residues, copper-containing residues, andcombinations thereof, said composition including at least one oxidizingagent, at least one oxidizing agent stabilizer comprising an aminespecies selected from the group consisting of primary amines, secondaryamines, tertiary amines and amine-N-oxides, optionally at least oneorganic co-solvent, optionally at least one metal-chelating agent,optionally at least one buffering species, and water, present in thefollowing ranges, based on the total weight of the composition.

component % by weight oxidizing agent(s) about 0.5% to about 20% aminespecies about 1% to about 25% organic co-solvent 0 to about 25 wt. %metal-chelating agent(s) 0 to about 1% buffer(s) 0 to about 5% waterabout 50% to about 99%

In the broad practice of the invention, the oxidizing cleaningcomposition may comprise, consist of, or consist essentially of: (i) atleast one oxidizing agent, optionally at least one oxidizing agentstabilizer comprising an amine species selected from the groupconsisting of primary amines, secondary amines, tertiary amines andamine-N-oxides, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water; (ii)at least one oxidizing agent, at least one oxidizing agent stabilizercomprising an amine species selected from the group consisting ofprimary amines, secondary amines, tertiary amines and amine-N-oxides,optionally at least one organic co-solvent, optionally at least onemetal-chelating agent, optionally at least one buffering species, andwater; (iii) at least one oxidizing agent, at least one oxidizing agentstabilizer comprising an amine species selected from the groupconsisting of primary amines, secondary amines, tertiary amines andamine-N-oxides, at least one organic co-solvent, optionally at least onemetal-chelating agent, optionally at least one buffering species, andwater; (iv) at least one oxidizing agent, at least one oxidizing agentstabilizer comprising an amine species selected from the groupconsisting of primary amines, secondary amines, tertiary amines andamine-N-oxides, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water; (v) atleast one oxidizing agent, at least one amine-N-oxide, optionally atleast one organic co-solvent, optionally at least one metal-chelatingagent, optionally at least one buffering species, and water; (vi)hydrogen peroxide, at least one amine-N-oxide, optionally at least oneorganic co-solvent, optionally at least one metal-chelating agent,optionally at least one buffering species, and water; (vii) hydrogenperoxide, at least one amine-N-oxide, at least one organic co-solvent,at least one metal-chelating agent, at least one buffering species, andwater; or (viii) hydrogen peroxide, optionally at least oneamine-N-oxide, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water.

The water is preferably deionized. When present, the organicco-solvent(s) are present in an amount from about 0.1 wt. % to about 25wt. %, the metal chelating agent(s) are present in an amount from about0.01 wt. % to about 1 wt. %, and the buffering species are present in anamount from about 0.01 wt. % to about 5 wt. %, based on the total weightof the composition.

In a preferred embodiment of the invention, the oxidizing aqueouscleaning composition is substantially devoid of abrasive material(s)typically found in chemical mechanical polishing (CMP) slurries, e.g.,silica, alumina, etc., when used to remove post-plasma etch residueand/or hardmask material from the microelectronic device having samethereon, i.e., when used to remove post-etch residue prior to subsequentdeposition or layering steps. “Substantially devoid” is defined hereinas less than 2 wt. %, preferably less than 1 wt. %, more preferably lessthan 0.5 wt. %, and most preferably less than 0.1 wt. %. However, it iscontemplated herein that the oxidizing aqueous cleaning composition mayinclude abrasive material(s) typically found in chemical mechanicalpolishing (CMP) slurries, e.g., silica, alumina, etc., for use inchemical mechanical polishing processes, e.g., Step II CMP processing.

It was surprisingly discovered that upon oxidation of the titanium (III)nitride to a titanium (IV) oxide species, the titanium (IV) species wasreadily soluble in a neutral composition, possibly because of theconcurrent presence of other species (e.g., silicon andoxygen-containing species) in the residue. Accordingly, in the broadpractice of the invention, the pH range of the oxidizing aqueouscleaning composition is about 3 to about 9, preferably about 6 to about9, and most preferably about 6.5 to about 8.5.

The oxidizing species contemplated herein include, but are not limitedto, hydrogen peroxide (H₂O₂), ferric nitrate (Fe(NO₃)₃), potassiumiodate (KIO₃), potassium permanganate (KMnO₄), nitric acid (HNO₃),ammonium chlorite (NH₄ClO₂), ammonium chlorate (NH₄ClO₃), ammoniumiodate (NH₄IO₃), ammonium perborate (NH₄BO₃), ammonium perchlorate(NH₄ClO₄), ammonium periodate (NH₄IO₃), ammonium persulfate((NH₄)₂S₂O₈), tetramethylammonium chlorite ((N(CH₃)₄)ClO₂),tetramethylammonium chlorate ((N(CH₃)₄)ClO₃), tetramethylammonium iodate((N(CH₃)₄IO₃), tetramethylammonium perborate ((N(CH₃)₄)BO₃),tetramethylammonium perchlorate ((N(CH₃)₄)ClO₄), tetramethylammoniumperiodate ((N(CH₃)₄)IO₄), tetramethylammonium persulfate((N(CH₃)₄)S₂O₈), urea hydrogen peroxide ((CO(NH₂)₂)H₂O₂), peracetic acid(CH₃(CO)OOH), and combinations thereof. Preferably, the oxidizing agentcomprises hydrogen peroxide. It is contemplated herein that theoxidizing agent, e.g., H₂O₂, may be added directly to the cleaningcomposition or generated in situ. One preferred aspect of the inventionrelates to a composition that comprises H₂O₂ and may be stored at least6 hours, more preferably at least 12 hours, even more preferably atleast 24 hours, prior to use.

The oxidizing agent stabilizer(s) comprises an amine species including,but not limited to: primary amines such as monoethanolamine,aminoethoxyethanol (diglycolamine), monoisopropanolamine,isobutanolamine, and C₂-C₈ alkanolamines; secondary amines such asmethylethanolamine, N-methylaminoethanol, and diethanolamine; tertiaryamines such as triethanolamine, methyldiethanolamine, triethylamine,N,N-dimethylglycolamine, N,N-dimethyldiglycolamine,pentamethyldiethylenetriamine; amine-N-oxides such asN-methylmorpholine-N-oxide (NMMO), trimethylamine-N-oxide,triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide,N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide; and substitutedderivatives or combinations thereof such as azoxy, oximes, oxaziranes,and oxazolidines. Preferably, the amine species includes NMMO.

Organic co-solvents contemplated herein include, but are not limited to,ethylene glycol, propylene glycol (PG), neopentyl glycol,1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol,formamide, acetamide, higher amides, N-methylpyrrolidone (NMP),N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane,dimethylsulfoxide (DMSO), γ-butyrolactone, propylene carbonate,diethylene glycol monomethyl ether, triethylene glycol monomethyl ether,diethylene glycol monoethyl ether, triethylene glycol monoethyl ether,ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,diethylene glycol monobutyl ether (i.e., butyl carbitol), triethyleneglycol monobutyl ether, ethylene glycol monohexyl ether, diethyleneglycol monohexyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, dipropylene glycol methyl ether, tripropylene glycolmethyl ether, propylene glycol n-propyl ether, dipropylene glycoln-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether, and combinationsthereof. Preferably, the organic co-solvent includes butyl carbitol,sulfolane, DMSO, and combinations thereof.

The optional metal-chelating agent(s) in the oxidizing aqueous cleaningcomposition of the invention is thought to minimize copper dissolutionwhich may be accelerated in the presence of the oxidizing agent(s) ofthe invention as well as to stabilize the oxidizing agent(s)-containingcomposition. The optional metal-chelating agent(s) may comprise one ormore components including for example, triazoles, such as 1,2,4-triazole(TAZ), or triazoles substituted with substituents such as C₁-C₈ alkyl,amino, thiol, mercapto, imino, carboxy and nitro groups, such asbenzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole,5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole,1-amino-1,2,4-triazole, hydroxybenzotriazole,2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole,1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole,3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole,5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br or I),naphthotriazole, and the like, as well as thiazoles, tetrazoles,imidazoles, phosphates, thiols and azines such as2-mercaptobenzoimidizole (MBI), 2-mercaptobenzothiazole,4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole(ATA), 5-amino-1,3,4-thiadiazole-2-thiol,2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,methyltetrazole, 1,3-dimethyl-2-imidazolidinone,1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol,5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate,indiazole, ethylenediaminetetraacetic acid (EDTA),1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA), andcombinations thereof. Preferably, the metal chelating-agent includes TAZand/or CDTA.

The optional buffering species may be included for pH stabilizationand/or selective removal of residues from exposed copper surfaces, e.g.,open vias. Preferably, the buffer includes tetralkylammonium salts ofweak acids, wherein the tetralkylammonium salt includes atetralkylammonium cation represented by [NR¹R²R³R⁴]⁺, where R¹, R², R³and R⁴ may be the same as or different from one another and are selectedfrom the group consisting of C₁-C₆ straight-chained or branched alkyl(e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl) or C₆-C₁₀substituted or unsubstituted aryl groups (e.g., benzyl), and the weakacid includes: boric acid; and a carboxylic acid such as lactic acid,maleic acid, ascorbic acid, malic acid, benzoic acid, fumaric acid,succinic acid, oxalic acid, malonic acid, mandelic acid, maleicanhydride, citric acid, phthalic acid, other aliphatic and aromaticcarboxylic acids, as well as combinations of the foregoing acids.Preferably, the buffering species includes a tetramethylammonium salt ofcitric acid or tetramethylammonium salts of boric acid.Tetraalkylammonium hydroxides that are commercially available may beused for production of the preferred tetralkylammonium salt of a weakacid in combination with the aforementioned acid species. For example,tetraethylammonium hydroxide (TEAH), tetramethyammonium hydroxide(TMAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammoniumhydroxide (TBAH) may be used. Tetraalkylammonium hydroxides which arenot commercially available may be prepared in a manner analogous to thepublished synthetic methods used to prepare TMAH, TEAH, TPAH and TBAH,which are known to one ordinary of skill in the art. Most preferably,the buffering species is included when metal chelating agent(s) arepresent to stabilize the pH of the composition so that the metal willnot erode and so that the peroxide does not decompose rapidly.

In addition, the oxidizing aqueous cleaning composition may furtherinclude surfactant(s), low-k passivator(s), etchant(s), defoamer(s),etc.

In various preferred embodiments, the oxidizing aqueous cleaningcomposition is formulated in the following Formulations A-W, wherein allpercentages are by weight, based on the total weight of the formulation:

Formulation A: 10.0% N,N-dimethyldiglycolamine; 5.0% hydrogen peroxide;85.0% waterFormulation B: 11.2% triethanolamine; 5.0% hydrogen peroxide; 83.8%waterFormulation C: 6.6% N,N-dimethylethanolamine; 5.0% hydrogen peroxide;88.4% waterFormulation D: 4.8% N-methylethanolamine; 5.0% hydrogen peroxide; 90.2%waterFormulation E: 8.3% N,N-dimethyldiglycolamine; 4.2% hydrogen peroxide;87.5% waterFormulation F: 8.3% NMMO; 4.2% hydrogen peroxide; 87.5% waterFormulation G: 0.1% TAZ; 8.3% NMMO; 4.2% hydrogen peroxide; 87.4% waterFormulation H: 0.1% 1,2,3-benzotriazole; 8.3% NMMO; 4.2% hydrogenperoxide; 87.4% waterFormulation I: 0.2% 1,2,4-triazole; 15% NMMO; 10% hydrogen peroxide; 10%diethylene glycol butyl ether; 0.45% citric acid; 0.55%tetramethylammonium hydroxide; 63.8% waterFormulation J: 0.2% 1,2,4-triazole; 7.5% NMMO; 1% hydrogen peroxide; 10%diethylene glycol butyl ether; 0.45% citric acid; 0.55%tetramethylammonium hydroxide; 80.3% waterFormulation K: 0.1% TAZ; 8.3% NMMO; 8.3% hydrogen peroxide; 81.4% waterFormulation L: 1.2% TAZ; 20% NMMO; 7.2% hydrogen peroxide; 63.4% waterFormulation M: 0.2% TAZ; 13.4% NMMO; 5% hydrogen peroxide; 10%diethylene glycol butyl ether; 71.4% waterFormulation N: 0.2% TAZ; 13.4% NMMO; 10% hydrogen peroxide; 10%diethylene glycol butyl ether; 66.4% waterFormulation O: 0.2% TAZ; 15% NMMO; 10% hydrogen peroxide; 10% diethyleneglycol butyl ether; 64.8% waterFormulation P: 0.2% 1,2,4-triazole; 15% NMMO; 1% hydrogen peroxide; 10%diethylene glycol butyl ether; 73.8% waterFormulation Q: 1% hydrogen peroxide; 7.5% NMMO; 10.0% butyl carbitol;0.2% 1,2,4-triazine; 0.45% citric acid; 0.55% tetramethylammoniumhydroxide; 80.3% waterFormulation R: 10% hydrogen peroxide; 7.5% NMMO; 10.0% butyl carbitol;0.2% 1,2,4-triazine; 0.45% citric acid; 0.55% tetramethylammoniumhydroxide; 71.3% waterFormulation S: 0.011% CDTA; 7.5% NMMO; 1.0% hydrogen peroxide; 10%diethylene glycol butyl ether; 0.52% boric acid; 0.22%tetramethylammonium hydroxide; 80.75% waterFormulation T: 0.2% 1,2,4-triazole; 1% hydrogen peroxide; 10% diethyleneglycol butyl ether; 0.45% citric acid; 0.55% tetramethylammoniumhydroxide; 87.8% waterFormulation U: 0.2% 1,2,4-triazole; 1% hydrogen peroxide; 10% diethyleneglycol butyl ether; 88.8% waterFormulation V: 1% hydrogen peroxide; 10.0% butyl carbitol; 0.2%1,2,4-triazine; 0.45% citric acid; 0.55% tetramethylammonium hydroxide;87.8% waterFormulation W: 0.011% CDTA; 1.0% hydrogen peroxide; 10% diethyleneglycol butyl ether; 0.52% boric acid; 0.22% tetramethylammoniumhydroxide; 88.25% water

In a preferred embodiment, the oxidizing aqueous composition of thepresent invention includes the following components present in thefollowing ranges, based on the total weight of the composition.

Component % by weight hydrogen peroxide about 2.5% to about 6.5%amine-N-oxide about 5% to about 10% metal-chelating agent(s) about 0.01%to about 0.5% Water balanceIn a particularly preferred embodiment of this invention, the oxidizingcleaning composition comprises hydrogen peroxide, NMMO, at least onemetal-chelating agent and water.

In another preferred embodiment, the oxidizing aqueous composition ofthe present invention includes the following components present in thefollowing ranges, based on the total weight of the composition.

Component % by weight hydrogen peroxide about 2.5% to about 12%amine-N-oxide about 5% to about 20% metal-chelating agent(s) about 0.01%to about 0.5% organic co-solvent(s) about 2% to about 15% Water about52.5 to about 91%In a particularly preferred embodiment of this invention, the oxidizingcleaning composition comprises hydrogen peroxide, NMMO, at least onemetal-chelating agent, at least one organic co-solvent, and water.

In yet another preferred embodiment of the present invention, theoxidizing aqueous composition of the present invention includes thefollowing components present in the following ranges, based on the totalweight of the composition.

Component % by weight hydrogen peroxide about 0.5% to about 12%amine-N-oxide about 5% to about 20% metal-chelating agent(s) about 0.01%to about 0.5% organic co-solvent(s) about 2% to about 15% acid/basebuffer(s) about 0.3 wt. % to about 2 wt. % water about 51.5 to about 91%In a particularly preferred embodiment of this invention, the oxidizingcleaning composition comprises hydrogen peroxide, NMMO, at least onemetal-chelating agent, at least one organic co-solvent, at least onebuffering species, and water. For example, the oxidizing cleaningcomposition may include 1,2,4-triazole, NMMO, hydrogen peroxide,diethylene glycol butyl ether, citric acid, tetramethylammoniumhydroxide and water. Alternatively, the oxidizing cleaning compositionmay comprise CDTA, NMMO, hydrogen peroxide, diethylene glycol butylether, boric acid, tetramethylammonium hydroxide, and water.

In still another preferred embodiment of the present invention, theoxidizing aqueous composition of the present invention includes at leastone oxidizing agent, at least one organic solvent, at least one metalchelating agent, at least one buffering species, and water. For example,the composition may include hydrogen peroxide, CDTA and borate ions(i.e., a tetralkylammonium salt and boric acid).

In another embodiment of the present invention, the oxidizing cleaningcomposition includes hydrogen peroxide, at least one oxidizing agentstabilizer comprising an amine species selected from the groupconsisting of primary amines, secondary amines, tertiary amines andamine-N-oxides, optionally at least one organic co-solvent, optionallyat least one metal-chelating agent, optionally at least one bufferingspecies, post-plasma etch residue, and water. Preferably, thepost-plasma etch residue comprises residue material selected from thegroup consisting of titanium-containing residue, polymeric-residue,copper-containing residue, and combinations thereof. In yet anotherembodiment of the present invention, the oxidizing cleaning compositionincludes hydrogen peroxide, at least one oxidizing agent stabilizercomprising an amine species selected from the group consisting ofprimary amines, secondary amines, tertiary amines and amine-N-oxides,optionally at least one organic co-solvent, optionally at least onemetal-chelating agent, optionally at least one buffering species,hardmask material, and water. Preferably, the hardmask material includestitanium-containing material residue. Importantly, the residue materialand/or hardmask material may be dissolved and/or suspended in thecleaning composition of the invention.

The TiN hardmask etch rate is strongly dependent on the concentration ofoxidizing agent species. If complete removal of the hardmask is notdesirable then a lower concentration of oxidizing agent(s) may be used,e.g., in a range from about 0.5 wt. % to about 3 wt. %, preferably about0.5 wt. % to about 1.5 wt. %. If complete removal of the hardmask is notdesirable, the range of weight percent ratios of the components of thecleaning composition are: about 1:1 to about 20:1 amine species relativeto oxidizing agent, more preferably about 2:1 to about 10:1; about 1:1to about 25:1 organic co-solvent(s) relative to oxidizing agent,preferably about 5:1 to about 15:1; about 0.01:1 to about 0.4:1 metalchelating agent(s) relative to oxidizing agent, preferably about 0.01:1to about 0.2:1; and about 0.01:1 to about 2:1 buffering agent(s)relative to oxidizing agent, preferably about 0.5:1 to about 1.5:1.

If on the other hand, complete removal of the hardmask is preferred, ahigher concentration of oxidizing agent(s) may be used, e.g., in a rangefrom about 5 wt. % to about 15 wt. %, preferably about 7.5 wt. % toabout 12.5 wt. %. If complete removal of the hardmask is desirable, therange of weight percent ratios of the components of the cleaningcomposition are: about 0.1:1 to about 5:1 amine species relative tooxidizing agent, more preferably about 0.75:1 to about 2:1; about 0.1:1to about 10:1 organic co-solvent(s) relative to oxidizing agent,preferably about 0.5:1 to about 2:1; about 0.01:1 to about 0.4:1 metalchelating agent(s) relative to oxidizing agent, preferably about 0.01:1to about 0.1:1; and about 0.01:1 to about 1:1 buffering agent(s)relative to oxidizing agent, preferably about 0.01:1 to about 0.5:1.

Concentrated oxidizing aqueous cleaning compositions may be diluted whenneeded (at the fab, etc.) by adding water to the cleaning compositionconcentrate. The cleaning composition is preferably diluted (water tocleaning composition) in a range from about 0.1:1 to about 20:1,preferably about 1:1 to about 10:1.

In addition to an aqueous solution, it is also contemplated herein thatthe oxidizing aqueous cleaning compositions may be formulated as foams,fogs, subcritical or supercritical fluids (i.e., wherein the solvent isCO₂, etc., instead of water).

The oxidizing aqueous cleaning compositions of the present inventionhave an extended bath-life relative to the peroxide-containing baths ofthe prior art. It is known that hydrogen peroxide-containingcompositions will decompose in the presence of trace amounts of metalions. Accordingly, the decomposition of hydrogen peroxide-containingcompositions can be minimized by adding metal ion chelators to thecleaning composition. Preferably, the percentage of peroxide measured at50° C. in a static oxidizing composition (i.e., no removal processingtherein) of the present invention after 24 hours is greater than about90% of the initial concentration, preferably greater than about 95%, andmost preferably greater than about 98%.

Further, said cleaning compositions preferably selectively removeshardmask and/or post-plasma etch residue from the top surface, thesidewalls, and the vias and lines of the microelectronic device withoutcompromising the ILD and/or the metal interconnect layers present on thedevice. Another advantage associated with the use of the presentinvention is that no post-clean bake step is necessary to removevolatile materials that may absorb into the pores of the ILD materials.

According to one embodiment, the cleaning composition provides an TiNhardmask etch rate greater than 25 Å min⁻¹, preferably greater than 50 Åmin⁻¹ and/or an TiN/Cu selectivity greater than 10:1, preferably greaterthan 20:1, more preferably greater than 50:1, even more preferablygreater than 100:1, even more preferably 200:1 and most preferablygreater than 250:1 when used at temperatures in a range from about 30°C. to about 60° C. Preferably, the compositions have the bath lifeand/or storage stability described herein thus providing a highlyselective cleaning composition with improved storage and usageproperties.

The oxidizing aqueous cleaning compositions of the invention are easilyformulated by simple addition of the respective ingredients and mixingto homogeneous condition. Furthermore, the oxidizing aqueous cleaningcompositions may be readily formulated as single-package formulations ormulti-part formulations that are mixed at the point of use, preferablymulti-part formulations. The individual parts of the multi-partformulation may be mixed at the tool or in a storage tank upstream ofthe tool. The concentrations of the respective ingredients may be widelyvaried in specific multiples of the oxidizing aqueous cleaningcomposition, i.e., more dilute or more concentrated, in the broadpractice of the invention, and it will be appreciated that the oxidizingaqueous cleaning compositions of the invention can variously andalternatively comprise, consist or consist essentially of anycombination of ingredients consistent with the disclosure herein.

Accordingly, another aspect of the invention relates to a kit including,in one or more containers, one or more components adapted to form thecompositions of the invention. Preferably, the kit includes, in one ormore containers, the preferred combination of at least one oxidizingagent stabilizer comprising an amine species selected from the groupconsisting of primary amines, secondary amines, tertiary amines andamine-N-oxides, at least one organic co-solvent, at least onemetal-chelating agent, at least one buffering species, and water forcombining with an oxidizing source at the fab or the point of use.According to another embodiment, the kit includes at least one tertiaryamine-containing additive, at least one organic co-solvent, at least onebuffering agent, at least one metal-chelating agent, and water, forcombining with and oxidizing source and water at the fab or the point ofuse. According to yet another embodiment, the kit includes at least oneamine-N-oxide, at least one organic co-solvent, at least one bufferingagent, at least one metal-chelating agent, and water, for combining withthe oxidizing source and water at the fab or the point of use. Accordingto yet another embodiment, the kit includes at least one amine-N-oxide,at least one organic co-solvent, at least one buffering agent, at leastone metal-chelating agent, and water, for combining with the oxidizingsource at the fab or the point of use. The containers of the kit must besuitable for storing and shipping said cleaning composition components,for example, NOWPak® containers (Advanced Technology Materials, Inc.,Danbury, Conn., USA).

As applied to microelectronic manufacturing operations, the oxidizingaqueous cleaning compositions of the present invention are usefullyemployed to clean post-plasma etch residue and/or titanium-containinghardmask from the surface of the microelectronic device, and may beapplied to said surface before or after the application of othercompositions formulated to remove alternative materials from the surfaceof the device. For example, a composition that preferentially removescopper-containing residues may be applied before or after the cleaningcomposition of the present invention is applied. Importantly, thecleaning compositions of the invention do not damage ILD materials onthe device surface and preferably remove at least 90% of the residueand/or hardmask present on the device prior to removal processing, morepreferably at least 95%, and most preferred at least 99%.

In post-plasma etch cleaning and/or titanium-containing hardmask removalapplication, the oxidizing aqueous cleaning composition is applied inany suitable manner to the device to be cleaned, e.g., by spraying theoxidizing aqueous cleaning composition on the surface of the device tobe cleaned, by dipping the device to be cleaned in a static or dynamicvolume of the oxidizing aqueous cleaning composition, by contacting thedevice to be cleaned with another material, e.g., a pad, or fibroussorbent applicator element, that has the oxidizing aqueous cleaningcomposition absorbed thereon, or by any other suitable means, manner ortechnique by which the oxidizing aqueous cleaning composition is broughtinto removal contact with the device to be cleaned. Further, batch orsingle wafer processing is contemplated herein.

In use of the compositions of the invention for removing post-plasmaetch residue from microelectronic devices having same thereon, theoxidizing aqueous cleaning composition typically is contacted with thedevice for a time of from about 1 minute to about 60 minutes, attemperature in a range of from about 25° C. to about 70° C., preferablyabout 30° C. to about 60° C. Such contacting times and temperatures areillustrative, and any other suitable time and temperature conditions maybe employed that are efficacious to at least partially remove thepost-etch residue material and/or hardmask layer from the device, withinthe broad practice of the invention. “At least partial removal” of theresidue material and/or hardmask layer from the microelectronic devicecorresponds to at removal of at least 90% of the material, preferably atleast 95% removal. Most preferably, at least 99% of said residuematerial and/or hardmask layer is removed using the compositions of thepresent invention.

Following the achievement of the desired removal action, the oxidizingaqueous cleaning composition, which is preferably water miscible, isreadily removed from the device to which it has previously been applied,e.g., by rinse, wash, or other removal step(s), as may be desired andefficacious in a given end use application of the compositions of thepresent invention. For example, the device may be rinsed with a rinsesolution including deionized water and/or dried (e.g., spin-dry, N₂,vapor-dry etc.).

Another aspect of the invention relates to a two-step method of removingpost-plasma etch residue material from the surface of themicroelectronic device. The first step involves the contacting of theoxidizing aqueous cleaning compositions of the invention with the devicefor a time of from about 1 minute to about 60 minutes, at temperature ina range of from about 25° C. to about 70° C., preferably about 30° C. toabout 60° C. Thereafter, the device is contacted with a dilutehydrofluoric acid composition at temperature in a range from about 20°C. to about 25° C. for 15 seconds to about 60 seconds. The dilutehydrofluoric acid composition may have a dilution in a range from about100:1 to about 1000:1 (water to HF), preferably about 400:1 to about600:1. Preferably, the device is rinsed with a rinse composition, e.g.,deionized water, subsequent to contact with the oxidizing aqueouscleaning composition and before contact with the dilute HF.

Yet another aspect of the invention relates to the improvedmicroelectronic devices made according to the methods of the inventionand to products containing such microelectronic devices.

A still further aspect of the invention relates to methods ofmanufacturing an article comprising a microelectronic device, saidmethod comprising contacting the microelectronic device with anoxidizing aqueous cleaning composition for sufficient time to cleanpost-plasma etch residue and/or titanium-containing hardmask from themicroelectronic device having said residue and/or material thereon, andincorporating said microelectronic device into said article, wherein theoxidizing aqueous cleaning composition includes at least one oxidizingagent, at least one oxidizing agent stabilizer comprising an aminespecies selected from the group consisting of primary amines, secondaryamines, tertiary amines and amine-N-oxides, optionally at least oneorganic co-solvent, optionally at least one metal-chelating agent,optionally at least one buffering species, and water.

In yet another embodiment, the oxidizing aqueous cleaning composition ofthe invention may be utilized in other aspects of the microelectronicdevice manufacturing process, i.e., subsequent to the post-plasma etchresidue cleaning step. For example, the oxidizing aqueous cleaningcompositions may be diluted and used as a post-chemical mechanicalpolishing (CMP) clean. Alternatively, the oxidizing aqueous cleaningcompositions of the present invention may be used to removecontaminating materials from photomask materials for re-use thereof.

In still another embodiment, the cleaning compositions of the inventionmay be combined with abrasive material and used as a Step II CMP slurry.Step II CMP slurries typically have a high barrier material removal raterelative to the removal rate of copper and dielectric material. Forexample, abrasive material may be added to the cleaning compositions ofthe invention (to yield a cleaning composition slurry) and used for theStep II CMP of a microelectronic device having tungsten and Ti/TiNbarrier layer materials thereon. If the microelectronic device comprisescopper material, a copper inhibiting species is preferably added to thecleaning composition slurry to protect the copper during planarizationprocesses. Abrasives contemplated herein includes silica, alumina, ceriaand mixtures thereof. Inhibitors contemplated herein include imidazole,aminotetrazole, benzotriazole, benzimidazole, 1,2,4-triazole,2-mercaptobenzimidazole (MBI), amino, imino, carboxy, mercapto, nitro,alkyl, urea and thiourea compounds, oxalic acid, malonic acid, succinicacid, nitrilotriacetic acid, iminodiacetic acid, and combinationsthereof.

The features and advantages of the invention are more fully illustratedby the following non-limiting examples, wherein all parts andpercentages are by weight, unless otherwise expressly stated.

Example 1

The etch rates of blanketed titanium nitride and physical vapordeposited (PVD) copper samples in Formulations A-D was determined. Thethickness of the TiN and PVD Cu coatings on silicon wafers were measuredbefore and after immersion for 60 minutes in Formulations A-D at theindicated temperatures. Thicknesses were determined using a 4-pointprobe measurement whereby the resistivity of the composition iscorrelated to the thickness of the film remaining and the etch ratecalculated therefrom. The experimental etch rates are reported in Table1.

TABLE 1 Etch rate of TiN and PVD Cu in Å min⁻¹ after immersion inFormulations A-D. Temperature/ Etch rate/Å min⁻¹ TiN/Cu Formulation ° C.TiN PVD Cu selectivity A 20 6.3 0.07 90:1 30 11.7 — — 40 18.7 — — B 2033.3 0.7 48:1 C 20 7.7 0.3 26:1 D 20 9.6 16.7 0.58:1  

It can be seen that at 20° C., Formulation A had the most favorable TiNto Cu etch selectivity. Further, the etch rate of TiN increased as thetemperature increased.

Example 2

A sample of low-k dielectric material consisting of a 3500 Å uniformcoating of porous CDO having a nominal k-value of 2.5 on a silicon waferwas evaluated for thickness and refractive index both before and afterimmersion in Formulation E for 10 minutes at 40° C. The thickness andrefractive index were measured using spectroscopic ellipsometry. Theresults are shown in Table 2 hereinbelow.

TABLE 2 Thickness and refractive index of blanketed porous CDO beforeand after immersion in Formulation E. pre-clean post-clean changethickness/Å 3265 3279 +14 refractive index 1.3693 1.3758 +0.0065

It can be seen that the neither the thickness nor the refractive indexchanged significantly following immersion of the porous CDO inFormulation E. This suggests that the CDO was not substantially etched,which is indicative of negligible change in the dielectric constant.

Referring to FIG. 2, which is the Fourier Transform Infrared (FTIR)Spectrograph of the porous CDO sample before and after immersion inFormulation E. It can be seen that no significant changes in thedifference spectrum obtained by subtraction of one spectrum from theother (time a factor of ten) is detectable, indicating that the porousCDO was not compromised by Formulation E.

A test sample was evaluated for cleaning using Formulation E. The testsample consisted of via and trench structures patterned in porous low-kCDO dielectric with a nominal k-value of 2.5. Low-k dielectric overcopper metal was exposed at the via bottoms. The dielectric was cappedby a 100 Å TiN layer over 400 Å silicon nitride or silicon oxynitridehardmask. Titanium-containing post-etch residue was present on the TiNlayer. The piece of the test sample was cleaned by static immersion inFormulation E for 15 minutes at 40° C. then rinsing with water.Evaluation by scanning electron microscopy (SEM) revealed completeremoval of titanium-containing residues and the titanium nitridehardmask layer with no observable changes or damage to the dielectricmaterial or corrosion of the copper layer.

Example 3

The bath-life of Formulation E was compared to the bath-life ofFormulation F by monitoring the concentration of hydrogen peroxide at40° C. The relative H₂O₂ concentration was measured for a solutionaliquot diluted in dilute sulfuric acid. The diluted aliquot wastitrated with a solution of about 7.5 w/v % ammonium cerium (IV) sulfatehydrate in dilute sulfuric acid. The relative H₂O₂ concentration wasdetermined by the volume ratio of cerium (IV) solution required to reachthe end point versus the volume required at zero aging time. The resultsof the bath-life comparison are shown in FIG. 3. It can be seen thatFormulation E, although a promising candidate for the selective andeffective removal of titanium-containing post-plasma etch residues,undergoes about 50% H₂O₂ decomposition over less than 50 minutes,thereby decreasing the efficacy of said formulation for the residuematerial over time. In contrast, Formulation F, comprising NMMO,underwent negligible decomposition over more than about 48 hours.

Example 4

The etch rates of blanketed titanium nitride and physical vapordeposited (PVD) copper samples in Formulations F-H was determined. Thethickness of silicon wafers having 1000 Å coatings of the respectivematerial were measured before and after immersion for 15 minutes at 50°C. in Formulations F-H as described hereinabove in Example 1. Theexperimental etch rates are reported in Table 3.

TABLE 3 Etch rate of TiN and PVD Cu in Å min⁻¹ after immersion inFormulations F-H. Etch rate/Å min⁻¹ TiN/Cu Formulation TiN PVD Cuselectivity F 25 1.8  14:1 G >50 0.2 >250:1 H — 0 —

It can be seen that at 50° C., Formulation G including NMMO had the mostfavorable TiN to Cu etch selectivity. Accordingly, a post-etchdual-damascene sample as described in Example 2 was cleaned by staticimmersion of the sample and the extent of cleaning determined by SEM,which revealed that the TiN was completely removed from the top surfaceand sidewalls of the device wafer. Further, the ILD and the copperinterconnect material was not damaged.

Example 5

A test sample was evaluated for cleaning using Formulation O. The testsample consisted of via and trench structures patterned in porous low-kCDO dielectric with a nominal k-value of 2.5. Low-k dielectric overcopper metal was exposed at the via bottoms. The dielectric was cappedby a 100 Å TiN layer over 400 Å silicon nitride or silicon oxynitridehardmask. Titanium-containing post-etch residue was present on the TiNlayer. The piece of the test sample was cleaned by static immersion inFormulation O for 6 minutes at 55° C. then rinsing with water.Evaluation by scanning electron microscopy (SEM) revealed completeremoval of titanium-containing residues, polymeric sidewall residues andTiN hardmask material with no observable changes or damage to thedielectric material, however, there was no observed removal of thecopper-containing residue, e.g., CuO, from the via bottoms.

To assist in the removal of the copper-containing residue, varyingamounts of buffering species were added to Formulation O. Theformulations tested are enumerated in Table 4.

TABLE 4 Variations of Formulation O having buffering species therein.PVD Cu Formulation buffer: base/acid ratio wt. % buffer pH ER/Å min⁻¹O-1 0.97 0.25 6.7 13.8 O-2 0.97 1.3 6.3 21.6 O-3 0.97 2.6 6.2 25.1 O-41.07 0.25 6.9 11.2 O-5 1.07 1.3 6.7 13.8 O-6 1.07 2.6 6.6 14.6 O-7 1.170.25 7.2 9.5 O-8 1.17 1.3 7.0 11.3 O-9 1.17 2.6 7.0 10.8 I 1.22 1 6.9not measured

As reported in Table 4, the etch rates of blanketed PVD copper sampleswas determined, wherein the thickness of the PVD Cu coating on a siliconwafer was measured before and after immersion for 60 minutes inFormulations O-1 through O-9 at 50° C. Thicknesses were determined usinga 4-point probe measurement whereby the resistivity of the compositionis correlated to the thickness of the film remaining and the etch ratecalculated therefrom. The experimental etch rates are illustrated inFIG. 4.

It can be seen in FIG. 4 that the copper etch rates are dependent onlyon the pH of the composition and not on the amount of buffer. As such,the pH of the composition is chosen so that the etch rate of copper isno more than 10 Å min⁻¹.

The aforementioned test sample was cleaned by static immersion inFormulation I for 4 minutes at 55° C. then rinsing with water. Aspreviously introduced, Formulation O, which is devoid of bufferingspecies, did not remove copper-containing residues from the bottom ofthe vias of the test sample. In contrast, Formulation I, which includesbuffering species, completely removed the TiN hardmask and thecopper-containing residue following immersion of the test sample in theformulation.

The post-clean capacitance of a sample of a porous carbon-doped oxide(CDO) dielectric with k-value of about 2.5 having the tradename BLACKDIAMOND® (BD2) was determined following immersion of blanketed BD2 inFormulation O and Formulation I at 55° C. for 5 minutes. The capacitancewas determined using a mercury probe tool with an impedance analyzer.Results are reported as an average of five measurements for each waferpiece. The results of the capacitance experiments are shown in FIG. 5.It can be seen that the capacitance of the BD2 wafer does notsubstantially increase following immersion in Formulation O orFormulation I, with the small increase within experimental error. Alsoillustrated in FIG. 5 is the change in tan δ, which is a measure of thedissipative loss in dielectric, which is also within experimental error.

Example 6

A test sample was evaluated for cleaning using Formulations J and P. Thetest sample consisted of via and trench structures patterned in porouslow-k CDO dielectric with a nominal k-value of 2.5. Low-k dielectricover copper metal was exposed at the via bottoms. The dielectric wascapped by a 100 Å TiN layer over 400 Å silicon nitride or siliconoxynitride hardmask. Titanium-containing post-etch residue was presenton the TiN layer.

One piece of the test sample was cleaned by static immersion inFormulation P for 6 minutes at 60° C. then rinsing with water.Evaluation by scanning electron microscopy (SEM) revealed completeremoval of surface residues, polymeric sidewall residues, partialremoval of copper-containing residues and minor TiN hardmask etching. Aspreviously discussed, if it is desirable to not remove the TiN hardmask,preferably the formulation includes a small amount of peroxide, e.g.,about 1 wt. % at in Formulation P.

The piece of the test sample was also cleaned by static immersion inFormulation J for 1.5 to 4.5 minutes at 40° C. or 50° C. then rinsingwith water. Evaluation by scanning electron microscopy (SEM) of thesample cleaned in Formulation J for 4.5 minutes at 40° C. revealednearly complete removal of surface residues, complete removal ofpolymeric sidewall residues, partial removal of copper-containingresidues and no TiN hardmask etching. Evaluation by scanning electronmicroscopy (SEM) of the sample cleaned in Formulation J for 3.0 minutesat 50° C. revealed nearly complete removal of surface residues, completeremoval of polymeric sidewall residues, complete removal ofcopper-containing residues and no TiN hardmask etching. In addition, nocopper interconnect damage was observed.

Example 7

Variations of Formulation S were analyzed to determine the decompositionrate of H₂O₂ at 60° C. with time relative to a control including just 1%H₂O₂ in an aqueous solution, as illustrated in FIG. 6. The formulationvariations include formulation S, formulation S plus Cu(NO₃)₂,formulation S plus Cu(C₂H₃O₂)₂, formulation S minus CDTA, formulation Sminus CDTA plus Cu(NO₃)₂, and formulation S minus CDTA plus Cu(C₂H₃O₂)₂.The concentration of the copper (II) salts ranged from 1 ppm to 10 ppm.In the experiments that formulation S was devoid of CDTA, theformulation was also devoid of boric acid, and TAZ and citric acid werepresent instead.

It can be seen in FIG. 6 that the presence of CDTA in the formulationextends the bathlife of the formulation to at least 24 hours, even inthe presence of a Cu²⁺ source such as Cu(NO₃)₂ and Cu(C₂H₃O₂)₂. Withoutthe CDTA, the composition immediately begins to undergo substantialdecomposition. Accordingly, the presence of CDTA stabilizes theoxidizing agent-containing bath, thus extending the lifetime of saidbath.

Referring to FIG. 7, it can be seen that the stability of the oxidizingagent-containing bath is further influenced by the pH of the bath.Comparing the results illustrated in FIG. 6 with those illustrated inFIG. 7, it can be seen that the ideal pH range when CDTA is the metalchelating agent and boric acid is one of the buffering species is about7.5 to about 8.5 while the ideal pH range when TAZ is the metalchelating agent and citric acid is one of the buffering species is about6 to about 6.5. As such, buffering species are preferred to maintain thepH in this useful range.

Example 8

A test sample was evaluated for cleaning using Formulation S. The testsample consisted of via and trench structures patterned in porous low-kCDO dielectric with a nominal k-value of 2.5. Low-k dielectric overcopper metal was exposed at the via bottoms. The dielectric was cappedby a 100 Å TiN layer over 400 Å silicon nitride or silicon oxynitridehardmask. Titanium-containing post-etch residue was present on the TiNlayer. The piece of the test sample was cleaned by static immersion inFormulation S for 5 minutes at 50° C. then rinsing with water.Evaluation by scanning electron microscopy (SEM) revealed completeremoval of titanium-containing residues from the TiN layer, partialremoval of the copper-containing residue, e.g., CuO, from the viabottoms, and no observable changes or damage to the dielectric materialor the TiN layer.

The same test sample was then evaluated for cleaning using a two-stepprocess—the first step involving static immersion in Formulation S for 4minutes at 50° C., and the second step involving static immersion in adilute hydrofluoric acid solution (400:1 water:HF) for 1 minute at 22°C. The sample was rinsed with deionized water between steps. SEMrevealed complete removal of titanium-containing residues from the TiNlayer, complete removal of the copper-containing residue from the viabottoms, and no observable changes or damage to the dielectric materialor the TiN layer. Importantly, a separate experiment involving a singlestep cleaning of the same wafer with dilute HF (400:1 water:HF) for 1minute at 22° C. revealed irregular copper etch loss. Accordingly, thetwo step process is favored when both titanium-containing residue andcopper-containing residue from the via bottoms is preferablysubstantially removed.

In addition, it is noted that an increased amount of oxidizing agent inthe formulation, e.g., 2 wt. % H₂O₂ instead of 1 wt. % H₂O₂, onlyincreases the etch rate of TiN and does not result in more efficientcleaning of the titanium-containing post-etch residue. Moreover, theremaining TiN layer had a greater surface roughness when exposed to theformulation having the higher H₂O₂ concentration.

The post-clean capacitance of BD2 sample was determined (1) followingimmersion of blanketed BD2 in Formulation S at 50° C. for 5 minutes, and(2) following immersion of blanketed BD2 in Formulation S at 50° C. for5 minutes following by immersion in dilute HF (400:1) for 1 minute at22° C. The capacitance was determined using a mercury probe tool with animpedance analyzer. It was determined that formulation S is compatiblewith the low-k dielectric layer.

Example 9

The etch rates of blanket PVD Cu wafers were measured followingimmersion of the Cu wafer in (1) Formulation S at 50° C., or (2) diluteHF at various dilutions (100:1, 200:1, 300:1, 400:1, 500:1, 600:1 and800:1) at 22° C. The etch rate of copper following immersion informulation S was determined to be about 2.6 Å min⁻¹ and the etch rateof copper following immersion in dilute HF was about 3-4 Å min⁻¹ andimportantly, was not strongly dependent on the extent of dilution.

Example 10

A test sample was evaluated for cleaning using Formulation S using atwo-step process—the first step involving static immersion inFormulation S for 5 minutes at 50° C., and the second step involvingstatic immersion in a dilute hydrofluoric acid solution (600:1 water:HF)for 0, 15, 30, 45, and 60 seconds at 22° C. The test sample consisted ofvia and trench structures patterned in porous low-k CDO dielectric witha nominal k-value of 2.5. Low-k dielectric over copper metal was exposedat the via bottoms. The dielectric was capped by a 100 Å TiN layer over400 Å silicon nitride or silicon oxynitride hardmask.Titanium-containing post-etch residue was present on the TiN layer.Evaluation by scanning electron microscopy (SEM) revealed completeremoval of titanium-containing residues from the TiN layer in each case.When the second step rinse was for 15 or 30 seconds, the copper wasclean without any observable undercut and when the second step rinse wasfor 45 or 60 seconds, the copper was clean however, some undercuttingwas observed especially at 60 seconds. As such, it was concluded that a30 second dilute HF clean was sufficient to clean copper residueswithout undercutting.

Although the invention has been variously disclosed herein withreference to illustrative embodiments and features, it will beappreciated that the embodiments and features described hereinabove arenot intended to limit the invention, and that other variations,modifications and other embodiments will suggest themselves to those ofordinary skill in the art, based on the disclosure herein. The inventiontherefore is to be broadly construed, as encompassing all suchvariations, modifications and alternative embodiments within the spiritand scope of the claims hereafter set forth.

1. An aqueous cleaning composition, comprising at least one oxidizingagent, at least one amine-N-oxide optionally at least one organicco-solvent, optionally at least one metal-chelating agent, optionally atleast one buffering species, and water, wherein the pH of the cleaningcomposition is about 3 to
 9. 2.-4. (canceled)
 5. The aqueous cleaningcomposition of claim 1, wherein the at least one oxidizing agentcomprises hydrogen peroxide.
 6. The aqueous cleaning composition ofclaim 1, wherein the amine-N-oxide comprises an species selected fromthe group consisting of N-methylmorpholine-N-oxide (NMMO),trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide,N-ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide,N-ethylpyrrolidine-N-oxide, and combinations thereof.
 7. (canceled) 8.The aqueous cleaning composition of claim 1, comprising Nmethylmorpholine-N-oxide.
 9. (canceled)
 10. The aqueous cleaningcomposition of claim 1, comprising the at least one metal chelatingagent, wherein the metal chelating agent comprises a compound selectedfrom the group consisting of 1,2,4-triazole (TAZ), benzotriazole,tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole,3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole,hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole,1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,halo-benzotriazoles, naphthotriazole, 2-mercaptobenzoimidizole,2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,2-mercaptothiazoline, 5-aminotetrazole,5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine,thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone,1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol,5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate,indiazole, ethylenediaminetetraacetic acid (EDTA),1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA), andcombinations thereof.
 11. The aqueous cleaning composition of claim 1,comprising at least one organic co-solvent, wherein said organicco-solvent comprises a species selected from the group consisting ofethylene glycol, propylene glycol (PG), neopentyl glycol,1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol,formamide, acetamide, higher amides, N-methylpyrrolidone (NMP),N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane,dimethylsulfoxide (DMSO), butyrolactone, propylene carbonate, diethyleneglycol monomethyl ether, triethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, triethylene glycol monoethyl ether, ethyleneglycol monopropyl ether, ethylene glycol monobutyl ether, diethyleneglycol monobutyl ether (i.e., butyl carbitol), triethylene glycolmonobutyl ether, ethylene glycol monohexyl ether, diethylene glycolmonohexyl ether, ethylene glycol phenyl ether, propylene glycol methylether, dipropylene glycol methyl ether, tripropylene glycol methylether, propylene glycol n-propyl ether, dipropylene glycol n-propylether (DPGPE), tripropylene glycol n-propyl ether, propylene glycoln-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycoln-butyl ether, propylene glycol phenyl ether, and combinations thereof.12. The aqueous cleaning composition of claim 1, comprising diethyleneglycol monobutyl ether.
 13. The aqueous cleaning composition of claim 1,comprising the at least one buffering species, wherein the bufferingspecies comprises a tetralkylammonium cation compound and an acid anioncompound, wherein the tetralkylammonium cation compound includes atetralkylammonium cation represented by the formula [NR¹R²R³R⁴]⁺, whereR¹, R², R³ and R⁴ may be the same as or different from one another andare selected from the group consisting of straight-chained C₁-C₆ alkyls,branched C₁-C₆ alkyls, substituted C₆-C₁₀ aryls, unsubstituted C₆-C₁₀aryls, and combinations thereof, and wherein the acid anion compound isselected from the group consisting of lactic acid, maleic acid, ascorbicacid, malic acid, benzoic acid, fumaric acid, succinic acid, oxalicacid, malonic acid, mandelic acid, maleic anhydride, citric acid,phthalic acid, boric acid other aliphatic and aromatic carboxylic acids,and combinations of the foregoing acids. 14.-15. (canceled)
 16. Theaqueous cleaning composition of claim 13, comprising a tetralkylammoniumsalt of citric acid or a tetralkylammonium salt of boric acid. 17.(canceled)
 18. The aqueous cleaning composition of claim 1, comprisingat least one organic co-solvent, at least one metal chelating agent, andat least one buffering species, wherein the aqueous cleaning compositioncomprises hydrogen peroxide, at least one amine-N-oxide, diethyleneglycol butyl ether, 1,2,4-triazole, tetramethylammonium hydroxide andcitric acid.
 19. The aqueous cleaning composition of claim 1, comprisingat least one organic co-solvent, at least one metal chelating agent, andat least one buffering species, wherein the aqueous cleaning compositioncomprises hydrogen peroxide, at least one amine-N-oxide, diethyleneglycol butyl ether, 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid,tetramethylammonium hydroxide and boric acid.
 20. (canceled)
 21. Theaqueous cleaning composition of claim 1, having a pH in a range fromabout 6 to about
 8. 22.-25. (canceled)
 26. A method of removingpost-plasma etch residue and/or hardmask material from a microelectronicdevice having said residue and/or hardmask thereon, said methodcomprising contacting the microelectronic device with an aqueouscleaning composition for sufficient time to at least partially cleansaid residue and/or hardmask from the microelectronic device, whereinthe aqueous cleaning composition includes at least one oxidizing agent,at least one amine-N-oxide, optionally at least one organic co-solvent,optionally at least one metal-chelating agent, optionally at least onebuffering species, and water, and wherein the pH of the cleaningcomposition is about 3 to
 9. 27.-30. (canceled)
 31. The method of claim26, wherein the at least one oxidizing agent comprises hydrogenperoxide; and wherein the at least one amine-N-oxide comprises an aminespecies selected from the group consisting of N-methylmorpholine-N-oxide(NMMO), trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide,N-ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide,N-ethylpyrrolidine-N-oxide, and combinations thereof.
 32. The method ofclaim 26, wherein said aqueous cleaning composition comprises at leastone metal chelating agent selected from the group consisting of1,2,4-triazole (TAZ), benzotriazole, tolyltriazole,5-phenyl-benzotriazole, 5-nitro-benzotriazole,3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole,hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole,1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,halo-benzotriazoles, naphthotriazole, 2-mercaptobenzoimidizole,2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,2-mercaptothiazoline, 5-aminotetrazole,5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine,thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone,1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol,5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate,indiazole, ethylenediaminetetraacetic acid (EDTA),1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA), andcombinations thereof.
 33. The method of claim 26, wherein the aqueouscleaning composition comprises at least one organic co-solvent selectedfrom the group consisting of ethylene glycol, propylene glycol (PG),neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol,glycerol, formamide, acetamide, higher amides, N-methylpyrrolidone(NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane,dimethylsulfoxide (DMSO), γ-butyrolactone, propylene carbonate,diethylene glycol monomethyl ether, triethylene glycol monomethyl ether,diethylene glycol monoethyl ether, triethylene glycol monoethyl ether,ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,diethylene glycol monobutyl ether (i.e., butyl carbitol), triethyleneglycol monobutyl ether, ethylene glycol monohexyl ether, diethyleneglycol monohexyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, dipropylene glycol methyl ether, tripropylene glycolmethyl ether, propylene glycol n-propyl ether, dipropylene glycoln-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether, and combinationsthereof.
 34. (canceled)
 35. The method of claim 26, wherein saidcomposition has a pH in a range of from about 6 to about
 8. 36.-38.(canceled)
 39. The method of claim 26, wherein the contacting comprisesa process selected from the group consisting of: spraying the aqueouscomposition on a surface of the microelectronic device; dipping themicroelectronic device in a sufficient volume of aqueous composition;contacting a surface of the microelectronic device with another materialthat is saturated with the aqueous composition; and contacting themicroelectronic device with a circulating aqueous composition.
 40. Themethod of claim 26, further comprising rinsing the microelectronicdevice with deionized water following contact with the aqueouscomposition.
 41. The method of claim 26, further comprising contactingthe microelectronic device with dilute hydrofluoric acid.
 42. (canceled)43. (canceled)